CN103907217B - The organic electroluminescent element - Google Patents

The organic electroluminescent element Download PDF

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CN103907217B
CN103907217B CN201280044173.2A CN201280044173A CN103907217B CN 103907217 B CN103907217 B CN 103907217B CN 201280044173 A CN201280044173 A CN 201280044173A CN 103907217 B CN103907217 B CN 103907217B
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aromatic
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carbon atoms
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多田匡志
甲斐孝弘
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新日铁住金化学株式会社
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    • H01L51/005Macromolecular systems with low molecular weight, e.g. cyanine dyes, coumarine dyes, tetrathiafulvalene
    • H01L51/0062Macromolecular systems with low molecular weight, e.g. cyanine dyes, coumarine dyes, tetrathiafulvalene aromatic compounds comprising a hetero atom, e.g.: N,P,S
    • H01L51/0071Polycyclic condensed heteroaromatic hydrocarbons
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    • H01L51/50Solid state devices using organic materials as the active part, or using a combination of organic materials with other materials as the active part; Processes or apparatus specially adapted for the manufacture or treatment of such devices, or of parts thereof specially adapted for light emission, e.g. organic light emitting diodes [OLED] or polymer light emitting devices [PLED];
    • H01L51/5012Electroluminescent [EL] layer
    • H01L51/5016Triplet emission

Abstract

本发明提供一种改善元件的发光效率同时充分确保驱动稳定性并且具有简单构成的有机电致发光元件(有机EL元件)。 The present invention provides a device to improve the light emission efficiency while sufficiently ensuring driving stability and having a simple configuration of an organic electroluminescence element (organic EL element). 该有机电致发光元件在层叠于基板上的阳极与阴极之间具有包含发光层的有机层,在有机层的至少1层中含有由下述式(1)表示的咔唑化合物。 The organic electroluminescence element having an organic layer including a light-emitting laminate layer between an anode and a cathode on a substrate, comprising a carbazole compound represented by the following formula (1) in at least one layer of the organic layer. 优选在发光层中含有上述咔唑化合物作为主体材料。 Preferably it contains the carbazole compound as a host material in the emission layer. 式(1)中,A为直接键合或者n价基团,E为氧或者硫,n为2~4的整数。 Formula (1), A is a direct bond or an n-valent group, E is oxygen or sulfur, n is an integer of 2 to 4.

Description

有机电致发光元件 The organic electroluminescent element

技术领域 FIELD

[0001] 本发明涉及有机电致发光元件,详细而言,涉及对由有机化合物形成的发光层施加电场而放出光的薄膜型器件。 [0001] The present invention relates to an organic electroluminescent device, more specifically, it relates to an electric field applied to the light-emitting layer formed of an organic compound and a thin-film device emitted light.

背景技术 Background technique

[0002] 通常,作为有机电致发光元件(以下,称为有机EL元件)的最简单的结构是由发光层和夹持该层的一对对置电极构成的。 [0002] Generally, the most simple structure as the organic electroluminescent device (hereinafter, referred to as organic EL element) is sandwiched by the light emitting layer and the layer of the pair of opposing electrodes. 即,在有机EL元件中,利用如下现象:在两电极间外加电场时,从阴极注入电子,从阳极注入空穴,这些电子和空穴在发光层中复合,放出光。 That is, in the organic EL element utilizing a phenomenon: when the applied electric field between the electrodes, electrons are injected from the cathode, holes are injected from the anode, the electrons and holes recombine in the emission layer, light is emitted.

[0003] 近年来,对使用了有机薄膜的有机EL元件进行了开发。 [0003] In recent years, an organic thin film using the organic EL element has been developed. 特别是为了提高发光效率, 以提高从电极注入载流子的效率为目的进行电极种类的最优化,开发在电极间以薄膜的形式设置由芳香族二胺形成的空穴输送层和由8-羟基喹啉铝配合物(以下,称为Alq 3)形成的发光层而成的元件,从而与以往使用了蒽等单晶的元件相比,发光效率得到了大幅度改善, 所以在应用于具有自发光•高速响应性的特征的高性能平板的目标中不断发展。 Particularly in order to improve the luminous efficiency, in order to improve the efficiency of injecting carriers from the electrodes to optimize the kind of electrodes for the purpose of developing a hole transporting layer of an aromatic diamine in the form of a thin film between the electrodes and from 8- hydroxyquinoline aluminum complex (hereinafter referred to as Alq 3) element formed on a light emitting layer formed so as to use conventional single crystal of anthracene and the like as compared element, light emission efficiency is greatly improved, so it applied having High-performance light emitting from the target plate • high-speed response characteristic in the development.

[0004] 另外,作为提高元件的发光效率的尝试,还研究了不使用荧光而使用磷光。 [0004] In another effort to enhance the luminous efficiency of the element, we were also studied using fluorescence without using phosphorescence. 虽然以上述设置了由芳香族二胺形成的空穴输送层和由Alq 3形成的发光层而成的元件为代表的大多数元件利用了荧光发光,但通过使用磷光发光,即,利用来自三重激发态的发光,期待与以往的使用荧光(单重态)的元件相比,提高3~4倍左右的效率。 Although most elements of the above-described elements provided with the hole transport layer is formed of an aromatic diamine and a light emitting layer formed by Alq 3 is formed by use of the fluorescent emission of the representative, but by the emission of light, i.e., use from the triplet luminescent excited state, as compared with expectations conventional elements using fluorescence (singlet state), increased by about 3-4 times more efficient. 为了达到该目的,研究了将香豆素衍生物、二苯甲酮衍生物制成发光层,但只能得到极低的亮度。 For this purpose, a study will be a coumarin derivative, a light-emitting layer benzophenone derivatives, but only at an extremely low luminance. 另外,作为利用三重态的尝试,研究了使用铕配合物,但这也达不到高效率的发光。 Further, attempts to use as a triplet, europium complexes were studied, but also reach a high efficiency of light emission. 近年来,如专利文献1所列举的那样,以发光的高效率化、长寿命化为目的,以铱配合物等有机金属配合物为中心进行了大量研究。 In recent years, as disclosed in Patent Document 1 mentioned above, a high light emission efficiency, long life object into, organometallic complexes of iridium complex like a number of studies as the center.

[0005] 现有技术文献 [0005] The prior art documents

[0006] 专利文献 [0006] Patent Document

[0007] 专利文献1:W001/041512 [0007] Patent Document 1: W001 / 041512

[0008] 专利文献2:日本特开2001-313178号公报 [0008] Patent Document 2: Japanese Patent Publication Laid-Open No. 2001-313178

[0009] 专利文献3:W02009/008100 [0009] Patent Document 3: W02009 / 008100

[0010] 专利文献4:W02005/057987 [0010] Patent Document 4: W02005 / 057987

[0011] 专利文献5:日本特开2005-132820号公报[0012] 专利文献6:日本特开2004-071500号公报 [0011] Patent Document 5: Japanese Patent Publication Laid-Open No. 2005-132820 [0012] Patent Document 6: Japanese Laid-Open Patent Publication No. 2004-071500

[0013] 为了得到高的发光效率,与上述掺杂剂材料同时使用的主体材料变得重要。 [0013] In order to obtain high luminous efficiency, a host material and the dopant material and use becomes important. 作为主体材料而提出的代表性的材料,可举出专利文献2中介绍的咔唑化合物4,4 双(9-咔唑基)联苯(以下,称为CBP)。 Representative materials as a host material proposed in Patent Document 2 may include a carbazole compound 4,4-bis (9-carbazolyl) biphenyl (hereinafter referred to as CBP). 将CBP用作以三(2-苯基吡啶)合铱配合物(以下,称为Ir(ppy)3) 为代表的绿色磷光发光材料的主体材料时,由于CBP容易流过空穴而难以流过电子的特性, 所以电荷注入平衡崩溃,过量的空穴流出到电子输送层侧,作为结果,来自Ir(ppy) 3的发光效率降低。 The CBP as tris (2-phenylpyridine) iridium complex (hereinafter referred to as Ir (ppy) 3) as the host material when the green phosphorescent light emitting material represented, since the CBP is difficult to flow easily flow through the holes through the characteristics of the electron, so the collapse of balance charge injection, the excess holes to flow out to the side of the electron transport layer, as a result, from the Ir (ppy) 3 of the light emission efficiency decreased.

[0014] 如上所述,为了在有机EL元件中得到高的发光效率,需要具有高的三重激发能并且两种电荷(空穴•电子)注入输送特性取得平衡的主体材料。 [0014] As described above, in order to obtain high luminous efficiency in the organic EL element is required to have high triplet excitation energy and charge (hole • electron) injection transport characteristics balance of the host material. 进而,期望电化学性稳定、同时具备高耐热性和优异的非晶稳定性的化合物,要求进一步的改良。 Further, it is desirable electrochemical stability, along with a compound having high heat resistance and excellent stability of the amorphous, require further improvement.

[0015]专利文献3中,作为有机EL元件的主体材料公开了以下所示的咔唑化合物。 [0015] Patent Document 3, as a host material for an organic EL element is disclosed a carbazole compound represented by the following.

Figure CN103907217BD00051

[0017]然而,该咔唑衍生物在二苯并呋喃的3,7位具有苯基,因此推断无法得到充分的发光效率。 [0017] However, the carbazole derivative having a phenyl group in the 3,7 position of dibenzofuran, thus inferring sufficient luminous efficiency can not be obtained.

[0018]专利文献4中,作为有机EL元件的主体材料公开了以下所示的咔唑化合物。 [0018] Patent Document 4, as a host material for an organic EL element is disclosed a carbazole compound represented by the following.

Figure CN103907217BD00052

[0020]专利文献5中,作为有机EL元件的主体材料公开了以下所示的咔唑化合物。 [0020] Patent Document 5, an organic EL device as a host material of a carbazole compound disclosed in the following FIG.

Figure CN103907217BD00053

[0022 ]然而,只公开了上述化合物在9位连接有咔唑的化合物。 [0022] However, only the above-mentioned compounds are disclosed in connection with a 9-carbazole.

[0023]专利文献6中,作为有机EL元件的主体材料公开了以下所示的咔唑化合物。 [0023] Patent Document 6, as a host material for an organic EL element is disclosed a carbazole compound represented by the following.

Figure CN103907217BD00054

[0025]然而,只公开了上述化合物在咔唑的9位导入了苯基的化合物,未公开使用在二苯并噻吩或二苯并呋喃的1位导入咔唑的化合物的有机EL元件的有用性。 Useful [0025] However, only compounds are disclosed in the above 9 introduced carbazole phenyl compounds, it does not disclose the use of dibenzothiophene or dibenzofuran introducing an organic EL element carbazole compound sex.

发明内容 SUMMARY

[0026]为了将有机EL元件应用于平板显示器等显示元件,需要在改善元件的发光效率的同时充分确保驱动时的稳定性。 [0026] For the organic EL devices to display devices such as flat panel displays, it is necessary to sufficiently secure the driving stability at the same time improving the efficiency of the light emitting element. 本发明鉴于上述现状,目的在于提供具有高效率且高驱动稳定性的在实用上有效的有机EL元件及适合它的化合物。 View of the foregoing situation, with an object to provide highly efficient and highly effective in driving the organic EL element on practical for stability and its compounds.

[0027]本发明人等进行深入研究,结果发现通过在有机EL元件中使用具有在二苯并噻吩或二苯并呋喃的1位与咔唑的N位键合的骨架并且在咔唑的3位的位置连接有2~4个该骨架的化合物,显示优异的特性,从而完成本发明。 [0027] The present inventors have conducted intensive studies and found that by using an organic EL element having a skeleton and the carbazole N bonds bonded dibenzothiophene or dibenzofuran and carbazole 3 bit positions 2-4 are connected to the backbone of the compound, exhibits excellent properties, thereby completing the present invention.

[0028]本发明涉及一种有机电致发光元件,其在基板上层叠阳极、有机层以及阴极而成, 其特征在于,在选自发光层、空穴输送层、电子输送层、空穴阻挡层以及电子阻挡层中的至少一层中使用了由通式(1)表示的咔唑化合物。 [0028] The present invention relates to an organic electroluminescence element which includes an anode, a cathode and an organic layer formed on the substrate, wherein the selected emission layer, a hole transport layer, an electron transporting layer, a hole blocking using the carbazole compound represented by the general formula (1) layer and an electron blocking layer is at least one.

Figure CN103907217BD00061

[0030] 通式(1)中,A是直接键合、-0-、-3-、-36-、地-、地-1?、>3丨-(1〇2、>66-(1〇2、碳原子数1~12的η价的脂肪族烃基、碳原子数3~12的η价的脂环式烃基、碳原子数6~18的η价的芳香族经基、碳原子数3~17的η价的芳香族杂环基、或者是2~4个芳香族环连接而成的η价基团,所述芳香族环选自碳原子数6~18的芳香族经环和碳原子数3~17的芳香族杂环,上述η 价的芳香族烃基、η价的芳香族杂环基或者上述芳香族环可以具有取代基。 [0030] Formula (1), A is a direct bond, from 0 -, - 3 -, --36-, the? -, to -1> Shu 3 - (1〇2,> 66- (1 〇2, η carbon atoms, divalent aliphatic hydrocarbon group having 1 to 12 carbon atoms, 3 to 12 η divalent alicyclic hydrocarbon group, the number of carbon atoms of 6 to 18 η divalent aromatic group via carbon atoms, η η divalent group monovalent aromatic heterocyclic group having 3 to 17, or 2 to 4 aromatic rings linked together, the number of carbon atoms of the aromatic ring via a ring selected from aromatic and 6 to 18 aromatic heterocycle having 3 to 17 carbon atoms, divalent aromatic hydrocarbon group described above [eta], [eta] a monovalent aromatic heterocyclic group, or the aromatic ring may have a substituent group.

[0031] R各自独立地表示碳原子数1~20的烷基、碳原子数1~20的环烷基、碳原子数6~ 18的芳香族经基、碳原子数3~17的芳香族杂环基。 [0031] R independently represents an alkyl group having 1 to 20 carbon atoms, the ring carbon atoms of the alkyl group having 1 to 20 carbon atoms, an aromatic group having 6 to 18 by aromatic having 3 to 17 carbon atoms heterocyclyl group.

[0032] R'各自独立地表示氢、碳原子数1~12的烷基、或者碳原子数1~12的烷氧基。 [0032] R 'each independently represent a hydrogen, an alkyl group of 1 to 12 carbon atoms or an alkoxy group having 1 to 12.

[0033] Ε表示氧或硫。 [0033] Ε represents oxygen or sulfur.

[0034] η表示2~4的整数。 [0034] η represents an integer of 2 to 4.

[0035] 通式(1)中,Α优选为如下基团中的任一个:直接键合、碳原子数1~6的η价的脂肪族经基、碳原子数3~8的η价的脂环式经基、上述η价的芳香族经基、上述η价的芳香族杂环基、或者2~4个上述芳香族环连接而成的η价基团。 [0035] Formula (1), preferably [alpha] is any one of the following groups: a direct bond, [eta] carbon atoms via a divalent aliphatic group of 1 to 6, carbon atoms [eta] 3-valent to 8 alicyclic group by the η divalent aromatic group via the η monovalent aromatic heterocyclic group, or a divalent group η 2 to 4 the aromatic ring linked together. 另外,更优选为如下基团中的任一个:直接键合、η价的芳香族烃基、η价的芳香族杂环基或者2~4个芳香族环连接而成的η价基团。 Further, more preferably the following groups in any one of: a direct bond, a divalent aromatic hydrocarbon group [eta], [eta] [eta] a divalent group or a divalent aromatic heterocyclic group having 2 to 4 aromatic rings linked together. [0036] 通式(1)中,η优选为2或3的整数。 In the [0036] Formula (1), η is preferably an integer of 2 or 3.

[0037]另外,上述有机电致发光元件优选具有含有由通式(1)表示的咔唑化合物和磷光发光掺杂剂的发光层。 [0037] Further, the above-described organic electroluminescence element having a luminescent layer preferably contains a carbazole compound and a phosphorescent dopant represented by the general formula (1).

附图说明 BRIEF DESCRIPTION

[0038] 图1是表示有机EL元件的一结构例的截面图。 [0038] FIG. 1 is a sectional view showing a configuration example of the organic EL element.

[0039] 图2表示咔唑化合物(1)的1H-NMR图。 [0039] FIG. 2 shows a carbazole compound (1) 1H-NMR of FIG.

[0040] 图3表示咔唑化合物(40)的1H-NMR图。 [0040] FIG. 3 shows a 1H-NMR chart carbazole compound (40).

具体实施方式 Detailed ways

[0041] 本发明的有机电致发光元件在特定的层中含有由上述通式(1)表示的咔唑化合物。 [0041] The present invention is an organic electroluminescent element comprising a carbazole compound represented by the general formula (1) in a particular layer. 在通式(1)中,A是直接键合或者η价基团,η为2、3或者LA是直接键合、-〇-、-S-、-Se-、> 1、地-1?、>5卜(1〇2、>66-(1〇2、碳原子数1~12优选1~6的11价的脂肪族烃基、碳原子数3~12 优选3~8的η价的脂环式经基、碳原子数6~18的η价的芳香族经基、碳原子数3~17的η价的芳香族杂环基、或者是2~4个芳香族环连接而成的η价基团,所述芳香族环选自碳原子数6 ~18的芳香族烃环和碳原子数3~17的芳香族杂环。 In the general formula (1), A is a direct bond or a divalent group [eta], [eta] is 2, 3 or LA is a direct bond, -〇 -, - S -, - Se -,> 1, -1 to? ,> 5 BU (1〇2,> 66- (1〇2, having 1 to 12 carbon atoms, preferably 11 monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms, preferably 3 to 12 η divalent aliphatic 3 to 8 by cyclic group, the number of carbon atoms of 6 to 18 η divalent aromatic group via the carbon atoms of 3 to 17 η monovalent aromatic heterocyclic group, or a 2-4 aromatic rings connected to each η divalent group, the aromatic ring carbon atoms selected from aromatic hydrocarbon ring and an aromatic heterocyclic ring having a carbon number 6 to 18 3 to 17.

[0042] 这里,上述η价的芳香族经基、η价的芳香族杂环基、芳香族经环以及芳香族杂环可以具有取代基,也可以不具有。 [0042] Here, the [eta] through divalent aromatic group, [eta] a monovalent aromatic heterocyclic group, an aromatic heterocyclic ring via a ring may have a substituent, and an aromatic group, or may not have.

[0043] 优选Α是直接键合、上述η价的脂肪族经基、上述η价的脂环式经基、上述η价的芳香族经基、上述η价的芳香族杂环基、或者2~4个上述芳香族环连接而成的η价基团。 [0043] preferably direct bond Α said η groups by divalent aliphatic, divalent above η alicyclic group by the η divalent aromatic group via the η monovalent aromatic heterocyclic group, or 2 to 4 the aromatic ring formed by connecting η monovalent group.

[0044] Α是碳原子数1~12的η价的脂肪族烃基的情况下,其可以为饱和也可以为不饱和, 可以为直链,也可以为支链。 [0044] Α case where η carbon atoms, a monovalent aliphatic hydrocarbon group of 1 to 12, which may be saturated or unsaturated, may be linear, may be branched. 作为具体例,可举出从甲烷、乙烷、乙烯、乙炔、丙烷、丙烯、丙炔、丁烷、丁烯、丁二烯、丁炔、戊烷、戊烯、戊炔、己烷、庚烷、辛烷、壬烷、癸烷等饱和或者不饱和的脂肪族烃中除去η个氢而得的η价基团等。 Specific examples may include from methane, ethane, ethylene, acetylene, propane, propene, propyne, butane, butene, butadiene, butyne, pentane, pentene, pentynyl, hexane, heptane saturated or unsaturated aliphatic hydrocarbon octane, nonane, decane, and the like obtained by removing one hydrogen η η monovalent group and the like. 优选为碳原子数1~6的η价的脂肪族烃基。 Η carbon atoms is preferably a divalent aliphatic hydrocarbon group having 1 to 6. 更优选为从由C mH2m+2表示的脂肪族烃中除去2~4个氢而生成的2~4价的脂肪族烃基。 More preferably 2 to 4 hydrogen is removed from an aliphatic hydrocarbon represented by C mH2m + 2 generated in 2 to 4 divalent aliphatic hydrocarbon group. 这里, m为1~6〇 Here, m is from 1 to 6〇

[0045] A为碳原子数3~12的η价的脂环式烃基的情况下,其可以为饱和也可以为不饱和, 可以为支链。 [0045] A case where the number of carbon atoms is 3 to 12 η divalent alicyclic hydrocarbon group, which may be saturated or unsaturated, may be branched. 作为具体例,可举出从环丙烷、环丁烷、环丁烯、环丁二烯、环戊烷、环戊烯、环己烷、甲基环己烷、环庚烷、环辛烷等饱和或者不饱和的脂环式烃中除去η个氢而得的η价基团等。 Specific examples include the cyclopropane, cyclobutane, cyclobutene, cyclobutadiene, cyclopentane, cyclopentene, cyclohexane, methylcyclohexane, cycloheptane, cyclooctane, etc. saturated or unsaturated alicyclic hydrocarbon obtained by removing one hydrogen η η monovalent group and the like. 优选为碳原子数3~8的η价的脂肪族烃基。 Η carbon atoms is preferably a divalent aliphatic hydrocarbon group having 3 to 8. 更优选为从由(:^^表示的脂环式烃中除去2~4个氢而生成的2~4价的脂肪族烃基。这里,m为3~8。 More preferably from the group consisting of (: removing 2 to 4 hydrogen ^^ alicyclic hydrocarbon represented by 2 to generate a tetravalent aliphatic hydrocarbon group here, m is 3-8.

[0046] A为碳原子数6~18的η价的芳香族经基或者碳原子数3~17的η价的芳香族杂环基的情况下,作为这些基团的具体例,可举出从选自苯、萘、芴、蒽、菲、焚蒽、芘、窟、吡啶、啼啶、三嗪、吲哚、喹啉、异喹啉、喹喔啉、萘啶、咔唑、吖啶、菲咯啉、吩嗪、苯并呋喃、二苯并呋喃、咕吨、二苯并对二ϊ»恶英(oxanthrene)、吩3恶嗪、苯并噻吩、二苯并噻吩、噻吨、噻蒽、吩巧I噻以及吩噻嗪的芳香族化合物中除去η个氢而生成的η价基团等。 Under [0046] the aromatic group via carbon atoms or carbon atoms and A is a divalent η η 6 to 18 3 to 17 divalent aromatic heterocyclic group is the case, specific examples of these groups include selected from benzene, naphthalene, fluorene, anthracene, phenanthrene, anthracene burning, pyrene, Cave, pyridine, piperidine cry, triazine, indole, quinoline, isoquinoline, quinoxaline, naphthyridine, carbazole, acridine , phenanthroline, phenazine, benzofuran, dibenzofuran, xanthene, dibenzo-p-ϊ »dioxin (oxanthrene), 3-oxazine thiophene, benzothiophene, dibenzothiophene, thioxanthone, thianthrene, removing generated hydrogen η η divalent group like I thiazole and thiophene aromatic compounds Qiao phenothiazine in. 优选为从选自苯、萘、 芴、蒽、菲、荧蒽、芘、窟、吡啶、嘧啶、三嗪、吲哚、喹啉、异喹啉、喹喔啉、萘啶、咔唑、吖啶、苯并呋喃、二苯并呋喃、吩0恶嗪、苯并噻吩、二苯并噻吩以及吩噻嗪的芳香族化合物中除去η 个氢而生成的η价基团。 Preferably selected from benzene, naphthalene, fluorene, anthracene, phenanthrene, fluoranthene, pyrene, Cave, pyridine, pyrimidine, triazine, indole, quinoline, isoquinoline, quinoxaline, naphthyridine, carbazole, acridine pyridine, benzofuran, dibenzofuran, thiophene 0 oxazine, benzothiophene, dibenzothiophene η η divalent groups formed by removing one hydrogen thiophene and the aromatic compound of phenothiazine generated. 更优选为从选自苯、吲哚、吡啶、嘧啶、三嗪、咔唑、苯并呋喃、二苯并呋喃、苯并噻吩以及二苯并噻吩的芳香族化合物中除去η个氢而生成的η价基团。 More preferably selected from benzene, indole, pyridine, pyrimidine, triazine, carbazole, benzofuran, dibenzofuran, benzothiophene and dibenzothiophene aromatic compound by removing one hydrogen generated η η monovalent group.

[0047] Α为2~4个芳香族环连接而成的η价基团且所述芳香族环选自碳原子数6~18的芳香族烃环和碳原子数3~17的芳香族杂环的情况下,作为上述芳香族烃环以及芳香族杂环, 有从A为碳原子数6~18的η价的芳香族烃基或者碳原子数3~17的η价的芳香族杂环基时所说明的芳香族化合物2~4个连接而生成的芳香族化合物中除去η个氢而生成的η价基团。 [0047] Α η is a divalent group having 2 to 4 aromatic rings linked together, and the aromatic ring is selected from aromatic hydrocarbon ring and carbon atoms 6 to 18 carbon atoms, an aromatic heteroaryl having 3 to 17 in the case of ring, the aromatic hydrocarbon ring and aromatic heterocyclic ring, or an aromatic hydrocarbon group having a carbon number of carbon atoms from the a-valent η η 6 to 18 3 to 17-valent aromatic heterocyclic group when described aromatic compound having 2 to 4 linked aromatic compound generated by removing η η monovalent radical hydrogen is generated.

[0048]作为给予上述芳香族环的芳香族化合物,优选苯、萘、芴、蒽、菲、荧蒽、芘、窟、吡啶、嘧啶、三嗪、吲哚、喹啉、异喹啉、喹喔啉、萘啶、咔唑、吖啶、苯并呋喃、二苯并呋喃、吩夂恶嗪、苯并噻吩、二苯并噻吩或者吩噻嗪。 [0048] As the aromatic compound is administered the aromatic ring, preferably benzene, naphthalene, fluorene, anthracene, phenanthrene, fluoranthene, pyrene, Cave, pyridine, pyrimidine, triazine, indole, quinoline, isoquinoline, quinoline , quinoxaline, naphthyridine, carbazole, acridine, benzofuran, dibenzofuran, thiophene Fan oxazine, benzothiophene, dibenzothiophene or phenothiazine. 更优选苯、吲哚、吡啶、嘧啶、三嗪、咔唑、苯并呋喃、 二苯并呋喃、苯并噻吩或者二苯并噻吩。 More preferably benzene, indole, pyridine, pyrimidine, triazine, carbazole, benzofuran, dibenzofuran, benzothiophene or dibenzothiophene.

[0049 ]这里,构成2~4个芳香族环连接而成的芳香族化合物的芳香族经环或者芳香族杂环可以相同,也可以不同,也可以含有芳香族烃环和芳香族杂环两者。 [0049] Here, by constituting the aromatic ring may be the same or an aromatic heterocyclic aromatic compound having 2 to 4 aromatic rings linked together, or may be different, and may contain an aromatic hydrocarbon ring and aromatic heterocycle two By. 作为2~4个上述芳香族环连接而成的芳香族化合物的具体例,例如可举出从联苯、三联苯、联吡啶、联嘧啶、联三嗪、双三嗪基苯、联萘、苯基吡啶、二苯基吡啶、二苯基嘧啶、二苯基三嗪、苯基咔唑、二苯基咔唑、二咔唑基苯、吡啶基咔唑、苯基二苯并呋喃或者苯基二苯并噻吩等中除去η个氢而生成的η价基团,键合位置没有限定,可以是末端的环,也可以是中央部的环。 Specific examples of the aromatic compound 2 to 4 the aromatic ring formed by connecting, for example, include from biphenyl, terphenyl, bipyridine, bipyrimidine, biphenyl triazine, bis triazine benzene, binaphthyl, phenyl pyridine, phenyl pyridine, pyrimidine diphenyl, diphenyl-triazine, carbazole phenyl, diphenyl carbazole, carbazole two phenyl, pyridyl carbazole, dibenzofuran phenyl or benzyl dibenzothiophene-yl and the like by removing one hydrogen generated η η divalent group, bonding position is not limited, and may be the end of the ring, the ring may be a central portion.

[0050] 上述芳香族烃环或者芳香族杂环与上述η价的芳香族烃基和η价的芳香族杂环基同样地可以具有取代基。 [0050] The aromatic hydrocarbon ring or an aromatic heterocyclic above η and η divalent aromatic hydrocarbon divalent aromatic heterocyclic group may have a substituent group in the same manner. η价的芳香族烃基、η价的芳香族杂环基、芳香族烃环或者芳香族杂环具有取代基的情况下,作为优选的取代基,可举出碳原子数1~12的烷基、碳原子数3~12 的环烷基、碳原子数1~12的烷氧基、碳原子数2~13的酰基或者碳原子数12~24的二芳基氨基。 [Eta] in the case of monovalent aromatic hydrocarbon group, [eta] a monovalent aromatic heterocyclic group, an aromatic hydrocarbon ring or an aromatic heterocyclic group having a substituent, preferable substituents include an alkyl group of 1 to 12 , a cycloalkyl group having 3 to 12 carbon atoms, an alkoxy group having a carbon number of 1 to 12 carbons, or an acyl group having 2 to 13 carbon atoms atoms diarylamino group having 12 to 24. 优选为碳原子数1~6的烷基、碳原子数3~8的环烷基、碳原子数1~6的烷氧基、碳原子数2~7的酰基或者碳原子数12~20的二芳基氨基。 Carbon atoms is preferably an alkyl group, a cycloalkyl group having 3 to 8 carbon atoms, carbon atoms, an alkoxy group having 1 to 6 carbon atoms or an acyl group having a carbon number of 2 to 12 7 to 20 1 to 6 diarylamino. 具有取代基的情况下,取代基的总数为1~10。 The case of a substituent group, the total number of substituent groups is 1 to 10. 优选为1~6,更优选为1~4。 Preferably 1 to 6, more preferably 1 to 4. 另外,上述芳香族烃基或者芳香族杂环基或者芳香环具有2个以上的取代基时,他们可以相同也可以不同。 Further, the aromatic hydrocarbon group or an aromatic heterocyclic group having an aromatic ring or two or more substituents, they may be the same or different. 另外,在上述芳香族烃基或者芳香族杂环基或者芳香环的碳原子数的计算中,具有取代基的情况下,不包含其取代基的碳原子数。 Further, in the calculation of the number of carbon atoms of the aromatic hydrocarbon group or an aromatic heterocyclic group, or an aromatic ring having a substituent, and it does not include the carbon number of the substituent. 芳香族烃基、芳香族杂环基或者芳香族环是取代芳香族烃基、取代芳香族杂环基或者取代芳香族环的情况下,其总计的碳原子数为取代芳香族烃基或者取代芳香族烃环的情况下,优选为6~50,更优选为6~30。 A case where an aromatic hydrocarbon group, an aromatic group or an aromatic heterocyclic ring is substituted by an aromatic hydrocarbon group, substituted aromatic group or substituted aromatic heterocyclic ring, the total number of carbon atoms of the substituted aromatic hydrocarbon or substituted aromatic hydrocarbon under a ring, preferably 6 to 50, more preferably 6 to 30. 是取代基芳香族杂环基或者取代芳香族芳香族环的情况下,其总计的碳原子数优选为3~50,更优选为4~30。 Substituent is an aromatic group or substituted aromatic heterocyclic aromatic ring, the total number of carbon atoms is preferably 3 to 50, more preferably 4 to 30.

[0051] 这里,由连接有2~4个芳香环的芳香族化合物生成的η价基团为2价基团的情况下,例如,由下述式表示。 [0051] Here, generated by connecting 2 to 4 aromatic rings η monovalent aromatic compound group is the case where the divalent group, for example, represented by the following formula.

Figure CN103907217BD00081

[0053] (An~Ar4表示芳香族环。) [0053] (An ~ Ar4 represents an aromatic ring.)

[0054] A为〉NR、>Si-(R)2或者〉Ge-(R)2时,R各自独立地表示碳原子数1~20的烷基、碳原子数1~20的环烷基、碳原子数6~18的芳香族烃基或者碳原子数3~17的芳香族杂环基,优选为碳原子数1~12的烷基、碳原子数1~12的环烷基、碳原子数6~12的芳香族烃基或者碳原子数3~12的芳香族杂环基。 [0054] A is> NR,> Si- (R) 2 or> Ge- (R) is 2, R each independently represents an alkyl group of 1 to 20 carbon atoms, a cycloalkyl group having 1 to 20 carbon atoms, the aromatic heterocyclic aromatic group having 3 to 17, or a hydrocarbon group having 6 to 18 carbon atoms, preferably carbon atoms, an alkyl group, having 1 to 12 carbon atoms, cycloalkyl group having 1 to 12 carbon atoms, aromatic hydrocarbon carbon atoms or an aromatic heterocyclic group having 6 to 12 3 to 12.

[0055] 作为碳原子数1~20的烷基、环烷基的具体例,可举出甲基、乙基、丙基、丁基、己基、庚基、辛基、壬基、癸基、环己基、甲基环己基等,可以为直链,也可以为支链。 [0055] As the alkyl group having 1 to 20 carbon atoms, and specific examples of the cycloalkyl group include methyl, ethyl, propyl, butyl, hexyl, heptyl, octyl, nonyl, decyl, cyclohexyl group, methylcyclohexyl group and the like, may be linear, it may be branched. 优选为甲基、乙基、丙基、丁基、戊基、己基、环己基。 Preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclohexyl.

[0056]作为碳原子数6~18的芳香族烃基、碳原子数3~17的芳香族杂环基的具体例,可举出从苯、萘、芴、蒽、菲、荧蒽、芘、窟、吡啶、嘧啶、三嗪、吲哚、喹啉、异喹啉、喹喔啉、萘啶、 咔唑、吖啶、菲咯啉、吩嗪、苯并呋喃、二苯并呋喃、咕吨、二苯并对二t*恶英、吩恶嗪、苯并噻吩、二苯并噻吩、噻吨、噻蒽、吩0悉噻、吩噻嗪等中除去氢而生成的基团等。 [0056] As aromatic hydrocarbon group having a carbon number of 6 to 18, specific examples of the aromatic heterocyclic group having 3 to 17 carbon atoms, and can include from benzene, naphthalene, fluorene, anthracene, phenanthrene, fluoranthene, pyrene, Cave, pyridine, pyrimidine, triazine, indole, quinoline, isoquinoline, quinoxaline, naphthyridine, carbazole, acridine, phenanthroline, phenazine, benzofuran, dibenzofuran, xanthene , t * dibenzo-p-dioxin, phenoxazine, benzothiophene, dibenzothiophene, thioxanthene, thianthrene, 0 thiophene noted thiophene, phenothiazine removing generated hydrogen radicals and the like. 优选为从苯、萘、 芴、蒽、菲、焚蒽、花、麓、啦啶、啼啶、三嗪、吲噪、喹啉、异喹啉、喹喔啉、萘啶身挫、叮啶、苯并呋喃、二苯并呋喃、吩恶嗪、苯并噻吩、二苯并噻吩、吩噻嗪等中除去氢而生成的基团,更优选为从苯、萘、蒽、菲、吡啶、嘧啶、三嗪、喹啉中除去氢而生成的基团。 Preferably from benzene, naphthalene, fluorene, anthracene, phenanthrene, burning anthracene, flowers, Lu, La piperidine, cry piperidine, triazine, indole noise, quinoline, isoquinoline, quinoxaline, naphthyridine body setback, bite piperidine , benzofuran, dibenzofuran, phenoxazine, benzothiophene, dibenzothiophene, phenothiazine removing generated hydrogen radicals, more preferably from benzene, naphthalene, anthracene, phenanthrene, pyridine, pyrimidine, triazine, quinoline groups formed by removing the hydrogen generated.

[0057]通式(1)中,R'各自独立地表示氢、碳原子数1~12的烷基或者碳原子数1~12的烷氧基,优选为氢、碳原子数1~6的烷基或者碳原子数1~6的烷氧基。 [0057] Formula (1), R 'each independently represents hydrogen, an alkyl group or a carbon atoms of 1 to 12 carbon atoms, an alkoxy group having 1 to 12, preferably hydrogen, carbon atoms and 1 to 6 alkyl group carbon atoms or an alkoxy group having 1 to 6. 作为烷基或者烷氧基的具体例,可举出甲基、乙基、丙基、丁基、己基、庚基、辛基、壬基、癸基、甲氧基、乙氧基、丙氧基、丁氧基等,烷基链可以是直链,也可以是支链。 Specific examples of the alkyl or alkoxy group include methyl, ethyl, propyl, butyl, hexyl, heptyl, octyl, nonyl, decyl, methoxy, ethoxy, propoxy group, butoxy group and the like, the alkyl chain may be linear, it may be branched. 优选为甲基、乙基、丙基、丁基、戊基、己基、甲氧基、乙氧基、丙氧基、丁氧基。 Preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, methoxy, ethoxy, propoxy, butoxy.

[0058] 通式(1)中,E表示氧或硫。 In the [0058] Formula (1), E represents oxygen or sulfur. η表示2~4的整数,优选为2或者3。 η represents an integer of 2 to 4, preferably 2 or 3.

[0059]由通式(1)表示的骨架中Ε由0表示的骨架以W02009-145016号公报所示的合成例作为参考,可以通过以下的反应式合成。 [0059] The skeleton represented by the general formula (1) is a skeleton represented by 0 Ε in Synthesis Example Publication No. W02009-145016 as shown by reference, may be synthesized by the following reaction formula.

Figure CN103907217BD00091

[0061]另外,Ε由S表示的骨架可通过以下的反应式合成。 [0061] Further, Ε skeleton represented by S can be synthesized by the following reaction formula.

Figure CN103907217BD00092

[0063] 通过利用例如铃木偶联等偶联反应将上述反应式中得到的各种化合物的碘取代于对应的连接基团上,能够合成由通式(1)表示的化合物。 [0063] By using a coupling reaction like Suzuki coupling e.g. iodine various compounds obtained by the above reaction formula to the corresponding substituted linking group, can be synthesized compound represented by the general formula (1).

[0064] 将由通式(1)表示的化合物的具体例在以下示出,但并不限定于这些例示化合物。 Specific examples of the compound [0064] by the general formula (1) are shown below, but are not limited to these exemplified compounds.

Figure CN103907217BD00101

Figure CN103907217BD00111

Figure CN103907217BD00121

Figure CN103907217BD00131

Figure CN103907217BD00141

[0070]通过在基板上层叠阳极、多个有机层以及阴极而成的有机EL元件的至少一个有机层中含有由上述通式(1)表示的咔唑化合物,能够获得优异的有机电致发光元件。 [0070] By containing the carbazole compound represented by the general formula (1) at least one organic layer includes an anode, a plurality of organic layers and the cathode of the organic EL element formed on the substrate, there can be obtained an excellent organic electroluminescent element. 作为含有咔唑化合物的有机层,发光层、空穴输送层、电子输送层或空穴阻挡层适合。 The organic layer containing the carbazole compound, a light emitting layer, a hole transport layer, an electron transporting layer or a hole blocking layer is adapted. 更优选含有其作为含有磷光发光掺杂剂的发光层的主体材料。 It more preferably contains a host material containing a light-emitting layer of a phosphorescent dopant.

[0071 ]接下来,对本发明的有机EL元件进行说明。 [0071] Next, an organic EL device of the present invention will be described.

[0072]本发明的有机EL元件,在层叠于基板上的阳极与阴极之间具有至少具有一个发光层的有机层,且至少一个有机层含有上述咔唑化合物。 [0072] The organic EL element of the present invention, the laminate having an organic layer having at least one light emitting layer between an anode and a cathode on a substrate, and at least one organic layer contains the carbazole compound. 优选在发光层中含有磷光发光掺杂剂和由通式(1)表示的咔唑化合物。 Preferably contains a phosphorescent dopant and carbazole compounds represented by the general formula (1) in the light-emitting layer.

[0073]接下来,参照附图对本发明的有机EL元件的结构进行说明,但本发明的有机EL元件的结构并不限定于任何图示。 [0073] Next, with reference to the accompanying drawings of the structure of the organic EL element of the present invention will be described, but the structure of the organic EL element of the present invention is not limited to any illustrated.

[0074]图1是表示通常的有机EL元件的结构例的截面图,1表示基板、2表示阳极、3表示空穴注入层、4表不空穴输送层、5表不发光层、6表不电子输送层、7表不阴极。 [0074] FIG. 1 is a sectional view showing a configuration example of a general organic EL element 1 represents a substrate, 2 represents an anode, 3 represents a hole injection layer, the hole transport layer 4 is not the table, the table is not a light emitting layer 5, Table 6 no electron transport layer 7 cathode table does not. 在本发明的有机EL元件中,也可以与发光层邻接地具有激子阻挡层,另外,在发光层和空穴注入层之间也可以具有电子阻挡层。 In the organic EL device of the present invention may also have the exciton-blocking layer adjacent to the light emitting layer. Further, between the light emitting layer and the hole injection layer may be an electron blocking layer. 激子阻挡层也可以插入到发光层的阳极侧、阴极侧中的任一侧,也可以同时插入双方。 Exciton blocking layer may be inserted into the anode side of the light emitting layer, either side of the cathode side, the two sides may also be inserted simultaneously. 在本发明的有机EL元件中,作为必须层具有基板、阳极、发光层以及阴极,但必须层以外的层可以具有空穴注入输送层、电子注入输送层,还可以在发光层与电子注入输送层之间具有空穴阻挡层。 In the organic EL device of the present invention, the layer must have a substrate, an anode, a cathode and a light emitting layer, the layer may be a layer other than the hole injecting and transporting layer having electron injection transport layer may also be injected in the light emitting layer and the electron transporting having a hole blocking layer between the layers. 应予说明,空穴注入输送层意味着空穴注入层和空穴输送层中的任一个或两者,电子注入输送层意味着电子注入层和电子输送层中的任一个或两者。 Incidentally, the hole injecting and transporting layer means a hole-injecting layer and a hole transport layer, or both, an electron injection and transport layer means that either or both of the electron injection layer and an electron transporting layer.

[0075] 应予说明,也可以采用与图1相反的结构,即,在基板1上依次层叠阴极7、电子输送层6、发光层5、空穴输送层4、阳极2,此时,也可以根据需要追加层或省略层。 [0075] Note that may be employed with the opposite configuration in FIG. 1, i.e., the substrate 1 are sequentially stacked on the cathode 7, the electron transport layer 6, luminescent layer 5, hole transport layer 4, an anode 2, at this time, also possible to add or omit layers layer.

[0076] -基板- [0076] - a substrate -

[0077] 本发明的有机EL元件优选被支撑于基板。 [0077] The organic EL element of the present invention is preferably supported on a substrate. 该基板没有特别限制,只要是以往惯用于有机EL元件的基板即可,例如可使用由玻璃、透明塑料、石英等形成的基板。 The substrate is not particularly limited as long as it is conventionally used for the organic EL element to a substrate, for example, using a substrate made of glass, transparent plastic, quartz or the like.

[0078]-阳极- [0078] - an anode -

[0079]作为有机EL元件中的阳极,优选使用功函数大的(4eV以上)金属、合金、导电性化合物以及它们的混合物作为电极物质的阳极。 [0079] As the anode of the organic EL element, preferably a large work function (4 eV or more) metal, an alloy, a conductive compound and a mixture thereof as an electrode substance of an anode. 作为这样的电极物质的具体例,可举出Au等金属、Cul、氧化铟锡(IT0)、Sn0 2、Zn0等导电性透明材料。 Specific examples of such an electrode material include a metal such as Au, Cul, indium tin oxide (IT0), Sn0 2, Zn0 and other conductive transparent material. 另外,也可以使用IDIX0(In203-Zn0)等为非晶且能够制作透明导电膜的材料。 Further, it may also be used IDIX0 (In203-Zn0), and can be produced as the amorphous transparent conductive film material. 对阳极而言,可以将这些电极物质利用蒸镀、 溅射等方法形成薄膜,用光刻法形成所需形状的图案,或者在不太需要图案精度的情况下(100μπι以上左右),也可以在蒸镀、溅射上述电极物质时介由所需形状的掩模形成图案。 Anode, these electrode materials may be vapor deposition, sputtering or the like forming a thin film pattern formed in a desired shape by photolithography, or in a case where not required pattern accuracy (100μπι more so), may be vapor deposition, sputtering of the electrode material is formed via a mask pattern of a desired shape. 或者,在使用如有机导电性化合物那样可以涂布的物质的情况下,也可以使用印刷方式、涂覆方式等湿式成膜法。 Alternatively, in the case of materials such as organic conductive compounds such as coated it may also be used a printing method, a wet coating method and other film-forming method. 在从该阳极取出发光时,优选透射率大于10%,并且作为阳极的薄层电阻(sheet resistance)优选为数百Ω/□以下。 When the light emission is extracted from the anode, preferably greater than 10% transmittance, and sheet resistance as an anode (sheet resistance) is preferably several hundred Ω / □ or less. 并且膜厚也取决于材料,但通常在10~ 1 OOOnm、优选在10~200nm的范围选择。 Depending on the material and the film thickness, but is usually selected in the range of 10 ~ 200nm 10 ~ 1 OOOnm, preferably.

[0080] -阴极_ [0080] - a cathode _

[0081] 另一方面,作为阴极,可使用功函数小的(4eV以下)金属(称为电子注入性金属)、 合金、导电性化合物以及它们的混合物作为电极物质的阴极。 [0081] On the other hand, as a cathode, small work function cathode can (4 eV or less) of metal (referred to as electron injecting metal), an alloy, a conductive compound and a mixture thereof as an electrode substance. 作为这样的电极物质的具体例,可举出钠、钠-钾合金、镁、锂、镁/铜混合物、镁/银混合物、镁/铝混合物、镁/铟混合物、 铝/氧化铝(Al 2〇3)混合物、铟、锂/铝混合物、稀土类金属等。 Specific examples of such electrode material include sodium, a sodium - potassium alloy, magnesium, lithium, a magnesium / copper mixture, a magnesium / silver mixture, a magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al 2 〇3) mixture, indium, a lithium / aluminum mixture, and a rare earth metal. 其中,从电子注入性以及对氧化等的耐久性的观点出发,优选电子注入性金属和功函数的值比其大的稳定的金属即第二金属的混合物,例如镁/银混合物、镁/铝混合物、镁/铟混合物、铝/氧化铝(Al 2〇3)混合物、锂/ 铝混合物、铝等适宜。 Among them, from the viewpoint of durability and electron injection property oxide, preferably a mixture of values ​​of injecting metal work function and greater than a second metal that is a stable metal, such as magnesium / silver mixture, a magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al 2〇3) mixture, lithium / aluminum mixture, or aluminum suitable. 阴极可以通过将这些电极物质利用蒸镀、溅射等方法形成薄膜来制作。 The cathode material can be produced by these electrodes by vapor deposition, sputtering or the like to produce a thin film is formed. 另外,作为阴极的薄层电阻优选为数百Ω/□以下,膜厚通常在l〇nm~5μπι、优选在50~ 200nm的范围选择。 Further, the sheet resistance as the cathode is preferably several hundreds Ω / □ or less, and a thickness generally in l〇nm ~ 5μπι, preferably in the range of 50 to 200nm is selected. 应予说明,为了使发出的光透过,有机EL元件的阳极或阴极中的任一者如果为透明或半透明则发光亮度提高而优选。 Note that, in order to make the light emitted through the anode or the cathode of the organic EL element, if any one is transparent or translucent to improve the emission luminance is preferable.

[0082]另外,通过在阴极将上述金属以1~20nm的膜厚成膜后,将在阳极的说明中举出的导电性透明材料在其上成膜,从而能够制作透明或半透明的阴极,通过应用该阴极,从而能够制作阳极和阴极两者具有透射性的元件。 [0082] Further, in the cathode by the deposition of the metal to the thickness of 1 ~ 20nm, the description will be exemplified in the anode of a transparent conductive material deposition thereon, it is possible to produce a transparent or translucent cathode by applying the cathode, thereby making both the anode and the cathode having a transmissive element.

[0083]-发光层- [0083] - light-emitting layer -

[0084] 发光层为磷光发光层,含有磷光发光掺杂剂和主体材料。 [0084] The light emitting layer is a phosphorescent light-emitting layer contains a phosphorescent dopant and a host material. 作为磷光发光掺杂剂材料,可以含有包含选自钌、铑、钯、银、铼、锇、铱、铂以及金中的至少一种金属的有机金属配合物。 As the phosphorescent dopant material may contain contain selected from ruthenium, rhodium, organometallic palladium, silver, rhenium, osmium, iridium, platinum, and at least one metal complex compound. 具体而言,可举出以下专利公报中记载的化合物,但并不限定于这些化合物。 Specific examples thereof include compounds described in the following patent publications, but is not limited to these compounds. 以下,记载专利公报等的编号。 The following describes number of patent publications.

[0085] W02009-073245号公报、W0 2009-046266号公报、W0 2007-095118号公报、W0 2008-156879号公报、W0 2008-140657号公报、US2008-261076号公报、日本特表2008-542203号公报、W0 2008-054584号公报、日本特表2008-505925号公报、日本特表2007-522126号公报、日本特表2004-506305号公报、日本特表2006-513278号公报、日本特表2006-50596号公报、W0 2006-046980号公报、W0 2005113704号公报、US2005-260449号公报、US2005-2260448号公报、US2005-214576号公报、W0 2005-076380号公报、US2005-119485号公报、W0 2004-045001 号公报、W0 2004-045000号公报、W0 2006-100888号公报、 TO 2007-004380号公报、W0 2007-023659号公报、W0 2008-035664号公报、日本特开2003- 272861号公报、日本特开2004-111193号公报、日本特开2004-319438号公报、日本特开2007- 2080号公报、日本特开2007-9009号公报、日本特开2007-227948号公报、日本特开2008- 91906号公报、日本特开2008-311607 [0085] Publication No. W02009-073245, Publication No. W0 2009-046266, Publication No. W0 2007-095118, 2008-156879 Publication No. W0, W0 2008-140657 Publication No., Publication No. US2008-261076, JP-A No. 2008-542203 Gazette, W0 No. 2008-054584, Japanese Patent Gazette No. 2008-505925, JP-A No. 2007-522126, and Japanese Patent Gazette No. 2004-506305, JP-A No. 2006-513278 and JP table 2006- Gazette No. 50596, W0 No. 2006-046980 Gazette, W0 No. 2005113704 Gazette, No. US2005-260449 Gazette, US2005-2260448 No. bulletin, No. US2005-214576 Gazette, W0 No. 2005-076380 Gazette, No. US2005-119485 Gazette, W0 2004- No. 045,001 Gazette, W0 No. 2004-045000 Gazette, W0 Gazette No. 2006-100888, TO No. 2007-004380 Gazette, W0 No. 2007-023659 Gazette, W0 No. 2008-035664, Japanese Patent Laid open No. 2003- 272861 and JP open No. 2004-111193, Japanese Patent Laid-open No. 2004-319438, Japanese Patent Laid-open No. 2007-2080, Japanese Patent Laid-open No. 2007-9009, Japanese Patent Laid-open No. 2007-227948, Japanese Unexamined Patent Publication No. 2008-91906 and Japanese Unexamined Patent 2008-311607 公报、日本特开2009-19121号公报、日本特开2009- 46601号公报、日本特开2009-114369号公报、日本特开2003-253128号公报、日本特开2003-253129号公报、日本特开2003-253145号公报、日本特开2005-38847号公报、日本特开2005-82598号公报、日本特开2005-139185号公报、日本特开2005-187473号公报、日本特开2005- 220136号公报、日本特开2006-63080号公报、日本特开2006-104201号公报、日本特开2006- 111623号公报、日本特开2006-213720号公报、日本特开2006-290891号公报、日本特开2006-298899号公报、日本特开2006-298900号公报、WO 2007-018067号公报、WO 2007/ 058080号公报、WO 2007-058104号公报、日本特开2006-131561号公报、日本特开2008-239565号公报、日本特开2008-266163号公报、日本特开2009-57367号公报、日本特开2002-117978号公报、日本特开2003-123982号公报、日本特开2003-133074号公报、日本特开2006-93542号公报、日 And Japanese Unexamined Patent Publication No. 2009-19121, Japanese Unexamined Patent Publication No. 2009-46601, Japanese Patent Laid-open No. 2009-114369, Japanese Patent Laid-open No. 2003-253128, Japanese Patent Laid-open No. 2003-253129, and Japanese Patent Laid-Open No. 2003-253145 and Japanese Unexamined Patent Publication No. 2005-38847, Japanese Unexamined Patent Publication No. 2005-82598, Japanese Patent Laid-open No. 2005-139185, Japanese Patent Laid-open No. 2005-187473, Japanese Unexamined Patent No. 220 136 Bulletin 2005- Japanese Unexamined Patent Publication No. 2006-63080, Japanese Patent Laid-open No. 2006-104201, and Japanese Patent Laid-open No. 2006- 111623, Japanese Patent Laid-open No. 2006-213720, Japanese Patent Laid-open No. 2006-290891, Japanese Unexamined 2006 No. -298,899, Japanese Patent Laid-open No. 2006-298900 Gazette, WO No. 2007-018067 gazette, WO 2007 / Bulletin No. 058 080, WO No. 2007-058104, Japanese Patent Laid-open No. 2006-131561, Japanese Unexamined Patent 2008-239565 No. bulletin, JP 2008-266163, Japanese Unexamined Patent Publication No. 2009-57367, Japanese Patent Laid-open No. 2002-117978, Japanese Patent Laid-open No. 2003-123982, Japanese Patent Laid-open No. 2003-133074 and JP open Gazette No. 2006-93542, Japanese 特开2006-131524号公报、日本特开2006-261623号公报、日本特开2006-303383号公报、日本特开2006-303394号公报、日本特开2006-310479号公报、日本特开2007-88105号公报、日本特开2007-258550号公报、日本特开2007-324309号公报、日本特开2008-270737号公报、日本特开2009-96800号公报、日本特开2009-161524号公报、 TO2008-050733号公报、日本特开2003-73387号公报、日本特开2004-59433号公报、日本特开2004-155709号公报、日本特开2006-104132号公报、日本特开2008-37848号公报、日本特开2008-133212号公报、日本特开2009-57304号公报、日本特开2009-286716号公报、日本特开2010-83852号公报、日本特表2009-532546号公报、日本特表2009-536681号公报、日本特表2009-542026号公报等。 Laid-open No. 2006-131524, Japanese Patent Laid-open No. 2006-261623, Japanese Patent Laid-open No. 2006-303383, Japanese Patent Laid-open No. 2006-303394, Japanese Patent Laid-open No. 2006-310479, and Japanese Patent Laid-Open 2007-88105 No. bulletin, JP 2007-258550, Japanese Patent Laid-open No. 2007-324309, Japanese Patent Laid-open No. 2008-270737, Japanese Unexamined Patent Publication No. 2009-96800, Japanese Patent Laid-open No. 2009-161524 Gazette, TO2008- No. 050,733, Japanese Patent Laid-open No. 2003-73387, Japanese Unexamined Patent Publication No. 2004-59433, Japanese Patent Laid-open No. 2004-155709, Japanese Patent Laid-open No. 2006-104132, Japanese Unexamined Patent Publication No. 2008-37848, Japanese Laid-open No. 2008-133212, Japanese Unexamined Patent Publication No. 2009-57304, Japanese Patent Laid-open No. 2009-286716, Japanese Unexamined Patent Publication No. 2010-83852, Japanese Patent Gazette No. 2009-532546, JP 2009-536681 No. bulletin, JP-A No. 2009-542026 bulletin and so on.

[0086]作为优选的磷光发光掺杂剂,可举出具有Ir等贵金属元素作为中心金属的Ir (ppy)3等配合物类、Ir(bt)2 · acac3等配合物类、Pt0Et3等配合物类。 [0086] Preferable phosphorescent dopants include Ir having a noble metal element such as Ir metal center of (ppy) 3 and the like based complex, Ir (bt) 2 · acac3 other complex species, Pt0Et3 like complexes class. 将这些配合物类的具体例在以下示出,但并不限定于下述化合物。 Specific examples of the species in these complexes are shown below, but are not limited to these compounds.

Figure CN103907217BD00171

[0089] 上述磷光发光掺杂剂在发光层中的含量优选为0.1~50重量%,更优选在1~30重量%的范围。 [0089] The content of the phosphorescent dopant in the light emitting layer is preferably 0.1 to 50 wt%, and more preferably in the range of 1 to 30% by weight.

[0090] 作为发光层中的主体材料,优选使用由上述通式(1)表示的咔唑化合物。 [0090] as a host material in the light emitting layer, preferably a carbazole compound represented by the general formula (1). 但是,在将该咔唑化合物用于发光层以外的其它任一有机层中的情况下,发光层所使用的材料也可以为咔唑化合物以外的其它主体材料。 However, in the case of a carbazole compound for any of the other layers than the organic light-emitting layer, the light emitting layer may also be used as a host material other than the carbazole compound. 另外,可以并用咔唑化合物和其它主体材料。 Further, the carbazole compound may be used, and other host materials. 并且, 也可以并用多种公知的主体材料。 And, it may be used in a variety of well-known host material.

[0091] 作为可使用的公知的主体化合物,优选为具有空穴输送能或电子输送能并且防止发光的长波长化、还具有高的玻璃化转变温度的化合物。 [0091] As is well-known host compounds may be used, preferably a hole-transporting or electron transporting ability, and can prevent the emission of longer wavelength, the compound also has a high glass transition temperature.

[0092] 这样的其它的主体材料,可通过许多专利文献等得知,所以可以从中选择。 [0092] Such other host materials, may be known by a number of patent documents, it is possible to choose from. 作为主体材料的具体例,没有特别限定,可举出吲哚衍生物、咔唑衍生物、吲哚并咔唑衍生物、三唑衍生物、#唑衍生物、鳴二唑衍生物、咪唑衍生物、聚芳基烷烃衍生物、吡唑啉衍生物、吡唑啉酮衍生物、苯二胺衍生物、芳胺衍生物、氨基取代查尔酮衍生物、苯乙烯基蒽衍生物、芴酮衍生物、腙衍生物、芪衍生物、硅氮烷衍生物、芳香族叔胺化合物、苯乙烯基胺化合物、芳香族二次甲基系化合物、扑啉系化合物、蒽醌二甲烷衍生物、蒽酮衍生物、二苯基醌衍生物、 噻喃二氧化物衍生物、萘并茈等杂环四羧酸酐、酞菁衍生物、以8-羟基喹啉衍生物的金属配合物、金属酞菁、苯并0恶唑或苯并噻唑衍生物的金属配合物为代表的各种金属配合物、聚硅烷系化合物、聚(N-乙烯基咔唑)衍生物、苯胺系共聚物、噻吩低聚物、聚噻吩衍生物、聚苯撑衍生物、聚苯 Specific examples of the host material is not particularly limited, and can include indole derivatives, carbazole derivatives, indole and carbazole derivatives, triazole derivatives, oxazole derivatives #, Ming oxadiazole derivatives, imidazole derivatives It was polyaryl alkane derivative, a pyrazoline derivative, a pyrazolone derivative, a phenylenediamine derivative, an arylamine derivative, an amino-substituted chalcone derivatives, styryl anthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic tertiary amine compounds, styrylamine compounds, aromatic dimethylidyne-based compound, flutter-based compound, an anthraquinodimethane derivative, anthrone derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, naphthalene and perylene and other heterocyclic tetracarboxylic acid anhydrides, phthalocyanine derivatives, 8-quinolinol metal complexes of derivatives, metal phthalocyanine phthalocyanine, a metal 0-benzo oxazole or benzothiazole derivative represented by complexes of various metal complex polysilane compounds, poly (N- vinylcarbazole) derivatives, aniline copolymers, thiophene low homopolymers, polythiophene derivatives, polyphenylene derivatives, polyphenylene 乙烯衍生物、聚芴衍生物等高分子化合物等。 Vinyl polymer compounds such derivatives, and polyfluorene derivatives.

[0093] -注入层- [0093] - injecting layer -

[0094] 注入层是指为了降低驱动电压、提高发光亮度而设置在电极与有机层之间的层, 有空穴注入层和电子注入层,可以存在于阳极与发光层或空穴输送层之间、以及阴极与发光层或电子输送层之间。 [0094] injecting layer means in order to reduce driving voltage and light emission luminance layer disposed between the electrode and the organic layer, a hole injection layer and an electron injection layer, it may be present in the anode and the emitting layer or the hole transport layer and , and between the cathode and the emitting layer or electron transporting layer. 注入层可以根据需要而设置。 Injection layer may be provided as required.

[0095]-空穴阻挡层- [0095] - a hole-blocking layer -

[0096] 空穴阻挡层广义上具有电子输送层的功能,由具有输送电子的功能同时输送空穴的能力非常小的空穴阻挡材料构成,通过输送电子的同时阻挡空穴,可以提高电子与空穴的复合概率。 Having [0096] the hole blocking layer generalized functional electron transport layer, a hole transport ability by having a function of transporting electrons while blocking holes of very small material, by transporting electrons while blocking holes and electrons can be improved the probability of recombination of holes.

[0097] 空穴阻挡层优选使用由通式(1)表示的咔唑化合物,但在其它任一有机层中使用咔唑化合物的情况下,也可以使用公知的空穴阻挡层材料。 In the case [0097] The hole blocking layer is preferably a carbazole compound represented by the general formula (1), but the use of a carbazole compound of any of the other organic layer may be a known hole blocking layer material. 另外,作为空穴阻挡层材料,可以根据需要使用后述的电子输送层的材料。 Further, as the hole transport layer may be a material in accordance with the need to use the electron-described barrier layer material.

[0098]-电子阻挡层- [0098] - electron blocking layer -

[0099] 电子阻挡层由具有输送空穴的功能的同时输送电子的能力非常小的材料构成,通过输送空穴的同时阻挡电子,从而可以确实地提高电子与空穴复合的概率。 Materials [0099] The electron blocking layer, electron transporting capability while having a function of transporting holes constituting very small, by transporting holes while blocking electrons, which can reliably increase the probability of recombination of electrons and holes.

[0100] 作为电子阻挡层的材料,可以根据需要使用后述的空穴输送层的材料。 [0100] As a material of the electron blocking layer, a hole transport layer material according to need after use to be described later. 电子阻挡层的膜厚优选为3~100nm,更优选为5~30nm〇 Electron blocking layer preferably has a thickness of 3 ~ 100nm, and more preferably 5 to 30nm〇

[0101] -激子阻挡层- [0101] - exciton blocking layer -

[0102] 激子阻挡层是用于阻挡空穴和电子在发光层内复合而生成的激子扩散到电荷输送层的层,通过本层的插入,从而可以将激子有效地封闭在发光层内,可以提高元件的发光效率。 [0102] exciton blocking layer for blocking holes and electrons are recombined in the emitting layer to generate an exciton diffusion layer of the charge transport layer, by inserting this layer, excitons can be effectively confined in the light-emitting layer within, the luminous efficiency can be improved. 激子阻挡层可以与发光层邻接地插入到阳极侧、阴极侧的任一侧,也可以同时插入其双方。 The exciton-blocking layer may be inserted adjacent to the light emitting layer to the anode side, on either side of the cathode side, both sides may be inserted simultaneously.

[0103] 作为激子阻挡层的材料,例如可举出1,3-二咔唑基苯(mCP)、双(2-甲基-8-羟基喹啉)-4_苯基苯酚铝(III) (BAlq)。 [0103] As a material of the exciton blocking layer, may include, for example, 1,3-carbazol-benzene (mCP), bis (2-methyl-8-quinolinolato) -4_ phenylphenolate aluminum (III ) (BAlq).

[0104]-空穴输送层- [0104] - hole transporting layer -

[0105] 空穴输送层由具有输送空穴的功能的空穴输送材料构成,空穴输送层可以设置单层或多层。 [0105] The hole transport layer is made of a material having a hole transporting function of transporting holes, a hole transport layer may be a single layer or multilayer provided.

[0106] 作为空穴输送材料,是具有空穴的注入或输送、电子的屏蔽性中的任一种功能的材料,可以为有机物、无机物中的任一种。 [0106] As the hole transporting material is a hole injecting or transporting material according to any one function in shielding an electronic, organic matter may be any one of inorganic substance. 优选在空穴输送层中使用由通式(1)表示的咔唑化合物,可以从以往公知的化合物中选择使用任意的化合物。 Preferably carbazole compound represented by the general formula (1) in the hole transporting layer, any compound may be selected from conventionally known compounds. 作为可使用的公知的空穴输送材料,例如可举出三唑衍生物、《恶二唑衍生物、咪唑衍生物、聚芳基烷烃衍生物、吡唑啉衍生物以及吡唑啉酮衍生物、苯二胺衍生物、芳胺衍生物、氨基取代查尔酮衍生物、0恶唑衍生物、苯乙烯基蒽衍生物、芴酮衍生物、腙衍生物、芪衍生物、硅氮烷衍生物、苯胺系共聚物、 以及导电性高分子低聚物、特别是噻吩低聚物等,优选使用三唑衍生物、0悉二唑衍生物、咪唑衍生物、芳胺衍生物,更优选使用芳胺衍生物。 Examples of the known hole transporting material may be used, for example, include triazole derivatives, "oxadiazole derivative, an imidazole derivative, a polyaryl alkane derivative, a pyrazoline derivative and a pyrazolone derivative , a phenylenediamine derivative, an arylamine derivative, an amino substituted chalcone derivative, 0 oxazole derivatives, styryl anthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives product, an aniline-based copolymer, and a conductive polymer oligomer, particularly a thiophene oligomer, preferably triazole derivatives, oxadiazole derivatives noted 0, imidazole derivatives, arylamine derivatives, more preferably aromatic amine derivative.

[0107]-电子输送层- [0107] - electron transporting layer -

[0108] 电子输送层由具有输送电子的功能的材料构成,电子输送层可以设置单层或多层。 [0108] The electron transport layer made of a material having a function of transporting electrons, the electron transporting layer may be a single layer or multilayer provided.

[0109] 作为电子输送材料(有时也兼作空穴阻挡材料),具有将从阴极注入的电子传送到发光层的功能即可。 [0109] As the electron transporting material (also sometimes function as a hole blocking material), has a function to transport electrons injected from the cathode to the light emitting layer. 电子输送层中优选使用本发明的由通式(1)表示的咔唑化合物,但可从以往公知的化合物中选择使用任意的化合物,例如可举出硝基取代芴衍生物、二苯基醌衍生物、噻喃二氧化物衍生物、碳化二亚胺、亚芴基甲烷衍生物、蒽醌二甲烷以及蒽酮衍生物、 夂恶二唑衍生物等。 The electron transporting layer is preferably used by the general formula (1) of the present invention represented carbazole compound, but may be any compound selected from conventionally known compounds, for example, include a nitro-substituted fluorene derivative, a diphenylquinone derivatives, thiopyran dioxide derivatives, carbodiimide derivatives, fluorenylidene methane, anthraquinodimethane and anthrone derivatives, oxadiazole derivatives Fan. 进而,在上述$恶二唑衍生物中,将0恶二唑环的氧原子置换成硫原子而得的噻二唑衍生物、具有作为吸电子基团而公知的喹喔啉环的喹喔啉衍生物也可用作电子输送材料。 Further, in the above-described $ oxadiazole derivative, an oxygen atom 0 oxadiazole ring is replaced with a sulfur atom thiadiazole derivatives obtained with an electron withdrawing group as the known quinoxaline quinoline ring Oh derivatives can be used as the electron transporting material. 还可以使用将这些材料导入高分子链而得的高分子材料,或以这些材料作为高分子的主链的高分子材料。 Use can also be introduced into a polymer chain obtained by a polymer material of these materials, or materials such as a polymer material backbone polymer.

[0110]以下,通过实施例进一步详细说明本发明,但本发明当然也不限定于这些实施例, 只要不超出本发明主旨,可以以各种方式实施。 [0110] Hereinafter, the embodiments of the present invention in further detail, but the present invention is of course not limited to these embodiments, without departing the gist of the present invention may be implemented in various ways.

[0111] 通过以下所示的路径合成成为磷光发光元件用材料的咔唑化合物。 [0111] Synthesis of phosphorescent light emitting element becomes carbazole compound material by the path shown below. 应予说明,化合物编号对应于上述例示化合物所标的编号。 Incidentally, the compound numbers correspond to the subject of the above-exemplified compounds numbers.

[0112] 实施例1 [0112] Example 1

[0113]化合物(1)的合成 [0113] Compound (1) Synthesis of

Figure CN103907217BD00201

[0115] 氮气氛下,加入2-甲氧基苯基硼酸18 · 84g(0 · 124mol)、1-溴-2,6-二氟苯24 · OOg (0.124111〇1)、四(三苯基膦)钯(0)7.728(0.00496111〇1)、甲苯6001111、乙醇1001111,在室温下边搅拌边加入2M氢氧化钠水溶液200ml。 Under [0115] nitrogen atmosphere, was added 2-methoxyphenylboronic acid 18 · 84g (0 · 124mol), 1- bromo-2,6-difluorophenyl 24 · OOg (0.124111〇1), tetrakis (triphenyl phosphine) palladium (0) 7.728 (0.00496111〇1), toluene, 6001111, 1001111 ethanol, stirring at room temperature is added with 2M aqueous sodium hydroxide solution 200ml. 在90°C搅拌5小时后,冷却至室温,用蒸馏水(300ml X 3)清洗有机层。 After stirring at 90 ° C for 5 hours and cooled to room temperature, the organic layer was washed with distilled water (300ml X 3). 将有机层用无水硫酸镁干燥后,滤出硫酸镁,减压馏去溶剂。 The organic layer was dried over anhydrous magnesium sulfate, and magnesium sulfate was filtered off, the solvent was distilled off under reduced pressure. 利用硅胶柱色谱法对得到的残渣进行精制,以白色固体的形式得到中间体(A1) 10.01g(0.0455mol,收率38%)〇 The resultant residue was purified by silica gel column chromatography, to give the intermediate (A1) 10.01g of a white solid (0.0455 mol, 38% yield) square

[0116] 氮气氛下,加入中间体(1)10.0(^(0.0454111〇1)、二氯甲烷1001111,在0°(:下边搅拌边加入三溴化硼的二氯甲烷溶液20ml。在室温下搅拌6小时后,加水。用蒸馏水(30ml X3)清洗有机层。将有机层用无水硫酸镁干燥后,滤出硫酸镁,减压馏去溶剂。利用硅胶柱色谱法对得到的残渣进行精制,得到作为无色液体的中间体(A2)8.62g(0.0418mol,收率92% )。 [0116] Under a nitrogen atmosphere, was added intermediate (1) 10.0 (^ (0.0454111〇1), 1,001,111 dichloromethane, at 0 ° (:. At room temperature with stirring 20ml of dichloromethane was added boron tribromide after stirring for 6 hours, water was added. the organic layer was washed with distilled water (30ml X3). the organic layer was dried over anhydrous magnesium sulfate, and magnesium sulfate was filtered off, the solvent was distilled off under reduced pressure. by silica gel column chromatography to give the residue was purified to give (A2) 8.62g (0.0418mol, 92% yield) as a colorless liquid intermediate.

[0117] 氮气氛下,加入中间体(A2)8.62g(0.0418mol)、N-甲基-吡咯烷酮230ml,在室温下边搅拌边加入碳酸钾11.56g(0.0836mol)。 Under [0117] nitrogen atmosphere, was added Intermediate (A2) 8.62g (0.0418mol), N- methyl - pyrrolidone 230 ml of, with stirring at room temperature was added potassium carbonate 11.56g (0.0836mol). 在180°C搅拌3小时后,冷却至室温,滤出碳酸钾。 After stirring at 180 ° C 3 hours, cooled to room temperature, potassium carbonate was filtered off. 在滤液中加入蒸馏水900ml,在室温下搅拌后,滤出所析出的固体。 900ml distilled water was added to the filtrate, after stirring at room temperature, the precipitated solid was filtered off. 使得到的固体溶解在二氯甲烷中,用蒸馏水(30ml X3)清洗有机层。 The obtained solid was dissolved in methylene chloride, the organic layer was washed with distilled water (30ml X3). 将有机层用无水硫酸镁干燥后,滤出硫酸镁,减压馏去溶剂。 The organic layer was dried over anhydrous magnesium sulfate, and magnesium sulfate was filtered off, the solvent was distilled off under reduced pressure. 利用硅胶柱色谱法对得到的残渣进行精制,以白色固体的形式得到中间体(A3)7.02g(0.0377mol,收率90%)。 The resultant residue was purified by silica gel column chromatography to give Intermediate (A3) 7.02g (0.0377mol, 90% yield) as a white solid.

[0119] 氮气氛下,加入咔唑35g(0.209mol)、乙酸300ml,在室温下边搅拌边加入碘化钾24 · 24g(0 · 146mol)、碘酸钾31 · 24g(0 · 146mol)。 Under [0119] nitrogen atmosphere, carbazole 35g (0.209mol), 300ml of acetic acid, potassium iodide was added with stirring 24 · 24g (0 · 146mol) at room temperature under iodate 31 · 24g (0 · 146mol). 在80°C搅拌2小时后,冷却至室温。 After stirring at 80 ° C for 2 hours and cooled to room temperature. 加入亚硫酸氢钠水溶液300ml、四氢呋喃300ml,在室温下搅拌。 Sodium bisulfite solution 300ml, tetrahydrofuran, 300ml, was stirred at room temperature. 加入甲苯300ml,用蒸馏水(200ml X 2) 清洗有机层。 Toluene was added 300ml, the organic layer was washed with distilled water (200ml X 2). 将有机层用无水硫酸镁干燥后,滤出硫酸镁,减压馏去溶剂。 The organic layer was dried over anhydrous magnesium sulfate, and magnesium sulfate was filtered off, the solvent was distilled off under reduced pressure. 利用重结晶对得到的残渣进行精制,以白色固体的形式得到中间体(A4)20.75g(0.0708mol)。 Recrystallization of the obtained residue was purified to give intermediate (A4) 20.75g (0.0708mol) as a white solid.

Figure CN103907217BD00211

[0120] 氮气氛下,加入氢化钠3.038(0.0752!11〇1)、二甲基甲酰胺(01^)201111,在室温下边搅拌边加入溶解有中间体以4)20.0(^(0.0682111〇1)的01^溶液201111。在室温下搅拌30分钟, 加入溶解有中间体(A3)7.00g(0.0376mol)的DMF溶液20ml。在120°C搅拌7小时后,冷却至室温。加入蒸馏水300ml在室温下搅拌。滤出所析出的固体。将得到的固体溶解在四氢呋喃中, 加入蒸馏水200ml。用甲苯(100ml X 3)萃取后,将有机层用无水硫酸镁干燥后,滤出硫酸镁, 减压馏去溶剂。利用硅胶柱色谱法对得到的残渣进行精制,以白色固体的形式得到中间体(A5) 16 · 74g(0 · 0364mol,收率97% )。 [0120] Under a nitrogen atmosphere, was added 3.038 of sodium hydride (0.0752! 11〇1), dimethylformamide (01 ^) 201 111, with stirring at room temperature was added dissolved in Intermediate 4) 20.0 (^ (0.0682111〇1 ) ^ 01 201111. DMF solution 20ml was stirred at room temperature for 30 minutes, then adding the intermediate (A3) 7.00g (0.0376mol) of after 120 ° C for 7 hours, cooled to room temperature in 300ml of distilled water was added stirred at room temperature. the precipitated solid was filtered off. the resulting solid was dissolved in tetrahydrofuran, 200ml distilled water was added. with toluene (100ml X 3) after extraction, the organic layer was dried over anhydrous magnesium sulfate, and magnesium sulfate was filtered off, Save the solvent was distilled pressure. the resultant residue was purified by silica gel column chromatography, to give intermediate (A5) 16 · 74g (0 · 0364mol, 97% yield) as a white solid.

[0121] 氮气氛下,加入氯化镍(II)六水合物4.16g(0.0152mol)、三苯基膦16.34g (0.0623mo 1)、二甲基甲酰胺50ml,进行脱气。 Under [0121] nitrogen atmosphere, was added nickel (II) chloride hexahydrate 4.16g (0.0152mol), triphenylphosphine 16.34g (0.0623mo 1), dimethylformamide 50ml, degassed. 加入锌1.29g(0.0198mo 1),在60 °C搅拌20分钟。 Zinc was added 1.29g (0.0198mo 1), stirred at 60 ° C 20 min. 加入溶解有中间体(A5) 5.84g(0.0127mo 1)的二甲基甲酰胺溶液50ml,在90 °C搅拌4小时。 Then adding the intermediate (A5) 5.84g (0.0127mo 1) of dimethylformamide was 50ml, was stirred at 90 ° C 4 hours. 将反应溶液冷却至室温,注入到水300ml中在室温下搅拌2小时。 The reaction solution was cooled to room temperature, poured into 300ml of water was stirred at room temperature for 2 hours. 滤出析出物,溶解在四氢呋喃中,加入水150ml。 The precipitate was filtered off, dissolved in tetrahydrofuran, was added water 150ml. 用甲苯50ml X 3进行萃取,将有机层用无水硫酸镁干燥后,滤出硫酸镁,减压馏去溶剂。 50ml X 3 with toluene, and the organic layer was dried over anhydrous magnesium sulfate, and magnesium sulfate was filtered off, the solvent was distilled off under reduced pressure. 利用硅胶柱色谱法、重结晶对得到的残渣进行精制,以白色固体形式得到化合物(1) 0 · 17g(0 · 000256mo 1,收率2 % )。 By silica gel column chromatography, recrystallization of the obtained residue was purified to give Compound (1) 0 · 17g (0 · 000256mo 1, 2% yield) as a white solid.

[0122] 将APCI-T0FMS、m/z 测定结果(测定溶剂:THF-d8)示于图2。 [0122] The APCI-T0FMS, m / z measurement result (measurement solvent: THF-d8) shown in FIG.

[0123] 实施例2 [0123] Example 2

[0124] 化合物(40)的合成 Synthesis of Compound [0124] (40)

Figure CN103907217BD00221

[0126] 在氮气氛下,加入(A5) 18 · 00g(0 · 0392mol)、联硼酸频那醇酯11 · 94g(0 · 0470mol)、 乙酸钾11.548(0.1176!11〇1),二甲基亚砜(0130)2001111,在60°(:搅拌30分钟。其后加入1,1'-双(二苯基膦)二茂铁-钯(II)二氯化物-二氯甲烷配合物0·96g(0·00118mo 1),在80°C搅拌6 小时后,冷却至室温。将冷却后的反应溶液注入到水中,在室温下搅拌6时间后,滤出所析出的固体。利用硅胶柱色谱法对得到的固体进行精制,以白色固体的形式得到中间体(A7) 9.99g(0.0217mol,收率55%)。 [0126] Under a nitrogen atmosphere, (A5) 18 · 00g (0 · 0392mol), with boronic acid pinacol ester 11 · 94g (0 · 0470mol), potassium acetate 11.548 (0.1176! 11〇1), dimethyl sulfoxide (0130) 2001111, at 60 ° (:. for 30 minutes followed by the addition of 1,1'-bis (diphenylphosphino) ferrocene - palladium (II) dichloride - dichloromethane complex 0.5 96g (0 · 00118mo 1), stirred at 80 ° C 6 hours, cooled to room temperature. the reaction solution after cooled was poured into water, stirred six hours at room temperature, filtered off the precipitated solid. using silica gel column chromatography the obtained solid was purified, to give intermediate (A7) 9.99g (0.0217mol, 55% yield) as a white solid.

[0127] 在氮气氛下,加入(△7)9.5(^(0.0207111〇1)、1,3-二碘苯3.1(^(0.0094111〇1)、四(三苯基膦)钯0.58g (0.000376mo 1)、甲苯300ml、乙醇50ml,在室温下边搅拌边加入2M氢氧化钠水溶液15ml后,在70 °C搅拌9小时。将反应溶液冷却至室温,用蒸馏水(100ml X 3)清洗有机层。将有机层用无水硫酸镁干燥后,滤出硫酸镁,减压馏去溶剂。利用硅胶柱色谱法、重结晶对得到的残渣进行精制,以白色固体的形式得到化合物(40)2.08g(0.00281mol,收率30%)〇 [0127] Under a nitrogen atmosphere, (△ 7) 9.5 (^ (0.0207111〇1), 1,3-diiodobenzene 3.1 (^ (0.0094111〇1), tetrakis (triphenylphosphine) palladium 0.58g (0.000376 after mo 1), toluene 300ml, ethanol 50ml, was added with stirring at room temperature 2M aqueous sodium hydroxide solution 15ml, was stirred at 70 ° C 9 h. the reaction solution was cooled to room temperature, the organic layer was washed with distilled water (100ml X 3). the organic layer was dried over anhydrous magnesium sulfate, and magnesium sulfate was filtered off, the solvent was distilled off under reduced pressure. by silica gel column chromatography, recrystallization of the obtained residue was purified to give the compound (40) as a white solid 2.08 g of ( 0.00281mol, 30% yield) square

[0128] 将APCI-T0FMS、m/z TAUM+iVH-NMR测定结果(测定溶剂:THF-d8)示于图3。 [0128] The APCI-T0FMS, m / z TAUM + iVH-NMR measurement (measurement solvent: THF-d8) shown in FIG.

[0129] 实施例3 [0129] Example 3

[0130] 在形成有膜厚llOnm的由ΙΤ0构成的阳极的玻璃基板上,用真空蒸镀法以真空度4.0Xl(T5Pa层叠各薄膜。首先,在ITO上以20nm的厚度形成CuPC。接下来,以20nm的厚度形成NTO作为空穴输送层。接下来,在空穴输送层上,由不同的蒸镀源共蒸镀作为主体材料的化合物(1)和作为掺杂剂的Ir(ppy)3,以30nm的厚度形成发光层。此时,Ir(ppy)3的浓度为10wt%。接着,以40nm的厚度形成Alq3作为电子输送层。进而,在电子输送层上以lnm的厚度形成氟化锂(LiF)作为电子注入层。最后,在电子注入层上以70nm的厚度形成铝(A1)作为电极,制作有机EL元件。 [0130] In the film thickness is formed on the ΙΤ0 llOnm glass substrate by anode constituted by a vacuum deposition method at a degree of vacuum 4.0Xl (T5Pa each laminated film. First, CuPC a thickness of 20nm is formed on the ITO. Next, to a thickness of 20nm is formed as NTO hole transporting layer. Next, on the hole transport layer by co-evaporation of different deposition sources as the host material of the compound (1) and as dopant Ir (ppy) 3, is formed to a thickness of 30nm light-emitting layer. the concentration of Ir (ppy) 3 is was 10wt%. Next, Alq3 was deposited to a thickness of 40nm as the electron transport layer. Further, a thickness of lnm fluoro formed on the electron transport layer lithium (LiF) as an electron injection layer. Finally, on the electron injection layer was formed to a thickness of 70nm aluminum (A1) as an electrode, an organic EL element.

[0131] 在得到的有机EL元件上连接外部电源、外加直流电压,结果确认具有表1那样的发光特性。 [0131] The organic EL element is connected to the external power source obtained, DC voltage is applied, having a light-emitting characteristics was confirmed as Table 1. 表1中,亮度、电压以及发光效率表示以20mA/cm 2驱动时的值。 In Table 1, the luminance, voltage, and luminous efficiency values ​​when driven at 20mA / cm 2. 可知元件发光光谱的极大波长为540nm,能够得到来自Ir(ppy)3的发光。 Found maximum wavelength of emission spectrum is 540nm, emission can be obtained from Ir (ppy) 3 in.

[0132] 实施例4~11 [0132] Examples 4 to 11

[0133] 与实施例1同样地合成化合物8、11、17、18、20以及31,作为实施例3的发光层的主体材料,代替化合物1而使用化合物8、11、17、18、20、31或者40,除此以外,与实施例3同样地制作有机EL元件。 [0133] the same manner as in Example 1 Synthesis of Compound 8,11,17,18,20 and 31, the light emitting layer as a host material of Example 3, was used instead of Compound 1 Compound 8,11,17,18,20, 31 or 40, except that, in the same manner as in Example 3 An organic EL device. 可知各元件发光光谱的极大波长为540nm,能够得到来自Ir(ppy)3的发光。 Found maximum wavelength of the emission spectrum of each of 540nm, emission can be obtained from Ir (ppy) 3 in.

[0134] 实施例12~13(比较) [0134] Examples 12 to 13 (Comparative)

[0135] 作为实施例3中的发光层的主体材料,使用CBP或者化合物H-1,除此以外,与实施例3同样地制作有机EL元件。 [0135] as a host material in the light emitting layer in Example 3 using CBP or a compound H-1, except that, in the same manner as in Example 3 An organic EL device. 元件发光光谱的极大波长为535nm(例12)或530nm(例13),认定能够得到来自Ir(ppy)3的发光。 The maximum wavelength of emission spectrum of 535 nm is (Example 12) or of 530 nm (Example 13), can be determined from the light emitting Ir (ppy) 3 in.

Figure CN103907217BD00231

[0139] 相对于实施例12和13 (比较),实施例3的初期特性提高。 [0139] increase with respect to Examples 12 and 13 (Comparative), Example 3 initial characteristics. 由此,可知通过在有机EL 元件使用在二苯并噻吩或二苯并呋喃的1位具有咔唑并且在咔唑的3位的位置具有特定取代基的化合物,有机EL元件特性得以改善。 Accordingly, it is understood by the organic EL element using dibenzothiophene or dibenzofuran and carbazole having a compound having a specific substituent at the 3 position of carbazole, an organic EL device characteristics are improved. 同样,实施例4~11的EL元件特性良好,在此也示出由通式(1)表示的咔唑化合物的优越性。 Also, excellent EL device characteristics embodiment Examples 4 to 11, here also shown advantages carbazole compound represented by the general formula (1).

[0140] 产业上的可利用性 [0140] INDUSTRIAL APPLICABILITY

[0141 ]本发明的有机电致发光元件中使用的由通式(1)表示的咔唑化合物通过在咔唑的3位连接2~4个在二苯并噻吩或二苯并呋喃的1位与咔唑的N位键合的骨架,从而认为能够进行空穴、电子迀移率的微调以及离子化电位(IP)、电子亲和力(EA)、三重态能量(T1)的各种能量值的控制。 [0141] The present invention has an organic electroluminescent carbazole compound represented by the formula used in the light emitting element (1) are connected by three in the 2 to 4 and dibenzo thiophene carbazole or dibenzofuran 1 and carbazole skeleton bonded to N bits, so that the hole can be performed, the electronic trim Gan shift rate and ionization potential (the IP), electron affinity (EA), the triplet energy (T1) of various energy values control. 另外,认为该咔唑化合物能够在氧化、还原、激发的各活性状态下提高稳定性,同时具有良好的非晶特性。 Further, the carbazole compound that is capable of oxidation, reduction, improve the stability of an active state in each excitation, while having good characteristics in the amorphous. 从以上方面考虑,可实现驱动寿命长、耐久性尚的有机EL 元件。 From the above viewpoint, it can realize long driving life, yet the durability of the organic EL element.

[0142]本发明的有机EL元件在发光特性、驱动寿命以及耐久性方面处于能满足实用的水平,在向平板板显示器(移动电话显示元件、车载显示元件、0A计算机显示元件、电视机等)、 利用作为面发光体的特征的光源(照明、复印机的光源、液晶显示器、仪器类的背光灯光源)、显示板、信号灯等的应用中,其技术价值大。 [0142] The organic EL element of the present invention is to meet a practical level in the light emission characteristics, driving life aspect, in the flat panel displays (mobile phone display devices, vehicle display devices, 0A computer display devices, television sets, etc.) , using a light source of the characteristics of planar light emitters (illumination, light sources of copiers, liquid crystal displays and instruments of the backlight light source), the application display panel, lights and the like, a large technical value.

Claims (5)

1. 一种有机电致发光元件,在基板上层叠阳极、有机层以及阴极而成,其特征在于,在选自发光层、空穴输送层、电子输送层以及空穴阻挡层中的至少一层中含有由通式(1)表示的咔唑化合物, An organic electroluminescence element, stacked on a substrate an anode, a cathode, and the organic layer is formed, characterized in that at least one selected from the light emitting layer, a hole transport layer, an electron transporting layer and the hole blocking layer layer containing a carbazole compound represented by the general formula (1),
Figure CN103907217BC00021
其中,A是碳原子数6~18的η价的芳香族经基、碳原子数3~17的η价的芳香族杂环基、 或者是2~4个芳香族环连接而成的η价基团,所述芳香族环选自碳原子数6~18的芳香族经环和碳原子数3~17的芳香族杂环,这里,该芳香族烃基、该芳香族杂环基、该芳香族烃环以及该芳香族杂环具有取代基或者不具有取代基; R '表不氢, E表示氧或者硫, η表示2~4的整数。 Wherein, A [eta] carbon atoms via a divalent aromatic group having 6 to 18, carbon atoms, [eta] [eta] 17 ~ 3 divalent aromatic heterocyclic group, or a 2-4 aromatic rings connected to each monovalent group, the aromatic ring carbon atoms selected from aromatic ring via carbon atoms and an aromatic heterocyclic 6 to 18 3 to 17, where the aromatic hydrocarbon group, the aromatic heterocyclic group, the aromatic aromatic hydrocarbon ring and an aromatic heterocyclic group having a substituent or no substituent group; R 'is not hydrogen table, E is oxygen or sulfur, η represents an integer of 2 to 4.
2. 根据权利要求1所述的有机电致发光元件,其中,通式(1)中,A是如下基团中的任一个:碳原子数3~17的η价的芳香族杂环基、或者2~4个芳香族环连接而成的η价基团,该芳香族环选自碳原子数3~17的芳香族杂环。 2. The organic electroluminescent device, wherein the general formula (1), A is any one of the following groups according to claim 1: η monovalent aromatic heterocyclic group having 3 to 17 carbon atoms, η or a divalent group having 2 to 4 aromatic rings linked together, the aromatic ring carbon atoms selected from an aromatic heterocycle having 3 to 17.
3. 根据权利要求2所述的有机电致发光元件,其中,A是如下基团中的任一个:η价的芳香族杂环基、或者2~4个芳香族环连接而成的η价基团,该芳香族环选自碳原子数3~17的芳香族杂环,η为2或3。 According to claim 2 in which the organic electroluminescent element, wherein, A is any one of the following groups: η monovalent aromatic heterocyclic group, or a 2-4 aromatic rings connected to each of the [eta] value group, the aromatic ring is selected from aromatic heterocycle having 3 to 17 carbon atoms, [eta] is 2 or 3.
4. 根据权利要求1~3中任一项所述的有机电致发光元件,其中,含有由通式(1)表示的咔唑化合物的层为含有磷光发光掺杂剂的发光层。 According to claim any one of the organic electroluminescent element 1 to 3, wherein the layer containing the carbazole compound represented by the general formula (1) is a light-emitting layer containing a phosphorescent dopant.
5. 根据权利要求1所述的有机电致发光元件,其中,由通式(1)表示的咔唑化合物为下示化合物中的任一个, 5. The organic electroluminescent device according to claim 1, wherein the carbazole compound represented by the general formula (1) shown below is a compound of any one,
Figure CN103907217BC00031
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